Catalyst modifier and its use in the polymerization of olefin(s)

ABSTRACT

The present invention relates to the use of at least one solid compound that when used with a polymerization catalyst in a polymerization process results in a phase change of the solid compound to a liquid that renders the polymerization catalyst substantially or completely inactive.

[0001] This application is a Divisional of U.S. patent application Ser.No. 09/392,417, filed Sep. 9, 1999, now issued as U.S. Pat. No. ______.

FIELD OF THE INVENTION

[0002] The present invention relates to a method for improvingoperability in a process for polymerizing olefin(s). In particular, theinvention is directed to a method for controlling the kinetics of anolefin polymerization catalyst.

BACKGROUND OF THE INVENTION

[0003] Advances in polymerization and catalysis have resulted in thecapability to produce many new polymers having improved physical andchemical properties useful in a wide variety of superior products andapplications. With the development of new catalysts the choice ofpolymerization-type (solution, slurry, high pressure or gas phase) forproducing a particular polymer has been greatly expanded. Also, advancesin polymerization technology have provided more efficient, highlyproductive and economically enhanced processes.

[0004] Especially illustrative of these advances is the development oftechnology utilizing bulky ligand metallocene-type catalyst systems.Regardless of these technological advances in the polyolefin industry,common problems, as well as new challenges associated with processoperability still exist. For instance, the tendency for a gas phase orslurry phase process to foul and/or sheet remains a challenge using anyolefin polymerization catalyst.

[0005] For example, in a continuous slurry process fouling on the wallsof the reactor, which act as a heat transfer surface, can result in manyoperability problems. Poor heat transfer during polymerization canresult in polymer particles adhering to the walls of the reactor. Thesepolymer particles can continue to polymerize on the walls and can resultin a premature reactor shutdown. Also, depending on the reactorconditions, some of the polymer may dissolve in the reactor diluent andredeposit on for example the metal heat exchanger surfaces.

[0006] In a typical continuous gas phase process, a recycle system isemployed for many reasons including the removal of heat generated in theprocess by the polymerization. Fouling, sheeting and/or staticgeneration in a continuous gas phase process can lead to the ineffectiveoperation of various reactor systems. For example, the cooling mechanismof the recycle system, the temperature probes utilized for processcontrol and the distributor plate, if affected, can lead to an earlyreactor shutdown.

[0007] Evidence of, and solutions to, various process operabilityproblems have been addressed by many in the art. For example, U.S. Pat.Nos. 4,792,592, 4,803,251, 4,855,370 and 5,391,657 all discusstechniques for reducing static generation in a polymerization process byintroducing to the process for example, water, alchols, ketones, and/orinorganic chemical additives; European Patent EP 0 634 421 B 1 discussesintroducing directly into the polymerization process water, alcohol andketones to reduce fouling. A PCT publication WO 97/14721 published Apr.24, 1997 discusses the suppression of fines that can cause sheeting byadding an inert hydrocarbon to the reactor; U.S. Pat. No. 5,627,243discusses a new type of distributor plate for use in fluidized bed gasphase reactors; PCT publication WO 96/08520 discusses avoiding theintroduction of a scavenger into the reactor; U.S. Pat. No. 5,461,123discusses using sound waves to reduce sheeting; U.S. Pat. No. 5,066,736and EP-A1 0 549 252 discuss the introduction of an activity retarder tothe reactor to reduce agglomerates; U.S. Pat. No. 5,610,244 relates tofeeding make-up monomer directly into the reactor above the bed to avoidfouling and improve polymer quality; U.S. Pat. No. 5,126,414 discussesincluding an oligomer removal system for reducing distributor platefouling and providing for polymers free of gels; EP-A1 0 453 116published Oct. 23, 1991 discusses the introduction of antistatic agentsto the reactor for reducing the amount of sheets and agglomerates; U.S.Pat. No. 4,012,574 discusses adding a surface-active compound, aperfluorocarbon group, to the reactor to reduce fouling; U.S. Pat. No.5,026,795 discusses the addition of an antistatic agent with a liquidcarrier to the polymerization zone in the reactor; U.S. Pat. No.5,410,002 discusses using a conventional Ziegler-Nattatitanium/magnesium supported catalyst system where a selection ofantistatic agents are added directly to the reactor to reduce fouling;U.S. Pat. Nos. 5,034,480 and 5,034,481 discuss a reaction product of aconventional Ziegler-Natta titanium catalyst with an antistat to produceultrahigh molecular weight ethylene polymers; U.S. Pat. No. 3,082,198discusses introducing an amount of a carboxylic acid dependent on thequantity of water in a process for polymerizing ethylene using atitanium/aluminum organometallic catalysts in a hydrocarbon liquidmedium; and U.S. Pat. No. 3,919,185 describes a slurry process using anonpolar hydrocarbon diluent using a conventional Ziegler-Natta-type orPhillips-type catalyst and a polyvalent metal salt of an organic acid.

[0008] There are various other known methods for improving operabilityincluding coating the polymerization equipment, for example, treatingthe walls of a reactor using chromium compounds as described in U.S.Pat. Nos. 4,532,311 and 4,876,320; injecting various agents into theprocess, for example PCT Publication WO 97/46599 published Dec. 11, 1997discusses feeding into a lean zone in a polymerization reactor anunsupported, soluble metallocene-type catalyst system and injectingantifoulants or antistatic agents into the reactor; controlling thepolymerization rate, particularly on start-up; and reconfiguring thereactor design.

[0009] Others in the art to improve process operability have discussedmodifying the catalyst system by preparing the catalyst 'system indifferent ways. For example, methods in the art include combining thecatalyst system components in a particular order; manipulating the ratioof the various catalyst system components; varying the contact timeand/or temperature when combining the components of a catalyst system;or simply adding various compounds to the catalyst system. Thesetechniques or combinations thereof are discussed in the literature.Especially illustrative in the art is the preparation procedures andmethods for producing bulky ligand metallocene-type catalyst systems,more particularly supported bulky ligand metallocene-type catalystsystems with reduced tendencies for fouling and better operability.Examples of these include: WO 96/11961 published Apr. 26, 1996 discussesas a component of a supported catalyst system an antistatic agent forreducing fouling and sheeting in a gas, slurry or liquid poolpolymerization process; U.S. Pat. No. 5,283,218 is directed towards theprepolymerization of a metallocene catalyst; U.S. Pat. Nos. 5,332,706and 5,473,028 have resorted to a particular technique for forming acatalyst by incipient impregnation; U.S. Pat. Nos. 5,427,991 and5,643,847 describe the chemical bonding of non-coordinating anionicactivators to supports; U.S. Pat. No. 5,492,975 discusses polymer boundmetallocene-type catalyst systems; U.S Patent No. 5 661,095 discussessupporting a metallocene-type catalyst on a copolymer of an olefin andan unsaturated silane; PCT publication WO 97/06186 published Feb. 20,1997 teaches removing inorganic and organic impurities after formationof the metallocene-type catalyst itself, PCT publication WO 97/15602published May 1, 1997 discusses readily supportable metal complexes; PCTpublication WO 97/27224 published Jul. 31, 1997 relates to forming asupported transition metal compound in the presence of an unsaturatedorganic compound having at least one terminal double bond; and EP-A2-811638 discusses using a metallocene catalyst and an activating cocatalystin a polymerization process in the presence of a nitrogen containingantistatic agent.

[0010] U.S. Pat. Nos. 4,942,147 and 5,362,823 discuss the addition ofautoacceleration inhibitors to prevent sheeting.

[0011] While all these possible solutions might reduce the level offouling or sheeting somewhat, some are expensive to employ and/or maynot reduce fouling and sheeting to a level sufficient to successfullyoperate a continuous process, particularly a commercial or large-scaleprocess.

[0012] Thus, it would be advantageous to have a polymerization processcapable of operating continuously with enhanced reactor operability andat the same time produce new and improved polymers. It would also behighly beneficial to have a continuously operating polymerizationprocess having more stable catalyst productivities, reducedfouling/sheeting tendencies and increased duration of operation.

SUMMARY OF THE INVENTION

[0013] This invention provides a method of making a new and improvedcatalyst composition, the catalyst composition itself and its use in apolymerizing process. Also, the invention is directed to the use of asubstantially solid, preferably a solid compound, that in the presenceof a polymerization catalyst at a specified temperature during apolymerization process undergoes a phase change where the solid compoundbecomes a liquid or gas, preferably a liquid, and the liquid or the gasrenders the polymerization catalyst substantially inactive, preferablyinactive, to the polymerization of olefin(s). The preferred compound isa polar compound having a low volatility, preferably an acid compound,specifically Bronsted acids.

[0014] The method comprises the step of combining, contacting, blendingand/or mixing any catalyst system, preferably a supported catalystsystem, with a compound, preferably with an acid compound such that at aspecified temperature the compound, preferably the acid compound,changes its physical state from a solid state to a liquid state, whereinthe liquid state deactivates the catalyst system. In the most preferredembodiment, the acid compound changes to a liquid state at a temperatureabove the polymerization temperature or reactor temperature. In oneembodiment, the catalyst system comprises a conventional-type transitionmetal catalyst compound. In the most preferred embodiment the catalystsystem comprises a bulky ligand metallocene-type catalyst compound. Thecombination or use of an olefin polymerization catalyst and thecompound, preferably the acid compound, is useful in any olefinpolymerization process. The preferred polymerization processes are a gasphase or a slurry phase process, most preferably a gas phase process.

[0015] In another preferred embodiment, the invention provides for aprocess for polymerizing olefin(s) in the presence of a polymerizationcatalyst, and a compound, preferably an acid compound, in a reactor atan operating temperature, wherein the compound, preferably the acidcompound, changes from a solid compound to a liquid compound at atemperature above the operating temperature reducing the effectivenessof the polymerization catalyst to polymerize olefin(s). In the mostpreferred embodiment, the liquid compound renders the polymerizationcatalyst inactive.

[0016] In yet another preferred embodiment, the invention is directed toa process for polymerizing olefin(s) in the presence of a polymerizationcatalyst in a reactor under polymerization conditions, the processcomprising the step of introducing a solid compound, preferably a solidacid compound; wherein the solid compound, preferably the solid acidcompound, becomes substantially a liquid, preferably a liquid acidcompound that reduces the effectiveness of the polymerization catalystto polymerize olefin(s).

DETAILED DESCRIPTION OF THE INVENTION

[0017] Introduction

[0018] The invention is directed toward a method for making a catalystcomposition and to the catalyst composition itself. The invention alsorelates to a polymerization process having improved operability usingthe catalyst composition. While not being bound to any particulartheory, it is believed that one possible cause for reduced operability,especially sheeting and/or fouling, is the result of a catalyst'stendency to continue to polymerize well after its initial activation. Ithas been suprisingly discovered that using a solid compound, preferablya solid acid compound, that undergoes a phase change to a substantiallya liquid state, preferably a liquid state, that in combination with apolymerization catalyst results in the ability to control the catalyst'stendency for continuing to effectively polymerize olefin(s). It has alsobeen discovered that the phase change is controllable by the choice ofthe compound used. In the most preferred embodiment, the temperature atwhich the phase change occurs is controlled by changing the acidcompound. The present invention is useful in all types of polymerizationprocesses, especially a slurry or gas phase process.

[0019] Catalyst Components and Catalyst Systems

[0020] All polymerization catalysts including conventional-typetransition metal catalysts and bulky ligand metallocene-type catalystsare suitable for use in the polymerizing process of the invention. Thefollowing is a non-limiting discussion of the various polymerizationcatalysts useful in the invention.

[0021] Conventional-Type Transition Metal Catalysts

[0022] Conventional-type transition metal catalysts are thosetraditional Ziegler-Natta catalysts and Phillips-type catalysts wellknown in the art. Examples of conventional-type transition metalcatalysts are discussed in U.S. Pat. Nos. 4,115,639, 4,077,904,4,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741 all of whichare herein fully incorporated by reference. The conventional-typetransition metal catalyst compounds that may be used in the presentinvention include transition metal compounds from Groups 3 to 17,preferably 4 to 12, more preferably 4 to 6 of the Periodic Table ofElements.

[0023] These conventional-type transition metal catalysts may berepresented by the formula: MR_(x), where M is a metal from Groups 3 to17, preferably Group 4 to 6, more preferably Group 4, most preferablytitanium; R is a halogen or a hydrocarbyloxy group; and x is the valenceof the metal M. Non-limiting examples of R include alkoxy, phenoxy,bromide, chloride and fluoride. Non-limiting examples ofconventional-type transition metal catalysts where M is titanium includeTiCl₄, TiBr₄, Ti(OC₂H₅)₃Cl , Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)₃Cl, Ti(OC₃H₇)₂Cl₂,Ti(OC₂H₅)₂Br₂, TiCl₃·1/3AL^(C)l₃ and Ti(OC₁₂H₂₅)Cl₃.

[0024] Conventional-type transition metal catalyst compounds based onmagnesium/titanium electron-donor complexes that are useful in theinvention are described in, for example, U.S. Pat. Nos. 4,302,565 and4,302,566, which are herein fully incorporate by reference. The MgTiCl₆(ethyl acetate)₄ derivative is particularly preferred.

[0025] British Patent Application 2,105,355 and U.S. Pat. No. 5,317,036,herein incorporated by reference, describes various conventional-typevanadium catalyst compounds. Non-limiting examples of conventional-typevanadium catalyst compounds include vanadyl trihalide, alkoxy halidesand alkoxides such as VOCl₃, VOCl₂(OBu) where Bu=butyl and VO(OC₂H₅)₃;vanadium tetra-halide and vanadium alkoxy halides such as VCl₄ andVCl₃(OBu); vanadium and vanadyl acetyl acetonates and chloroacetylacetonates such as V(AcAc)₃ and VOCl₂(AcAc) where (AcAc) is an acetylacetonate. The preferred conventional-type vanadium catalyst compoundsare VOCl₃, VCl₄ and VOCl₂-OR where R is a hydrocarbon radical,preferably a C₁ to C₁₀ aliphatic or aromatic hydrocarbon radical such asethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl,tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetylacetonates.

[0026] Conventional-type chromium catalyst compounds, often referred toas Phillips-type catalysts, suitable for use in the present inventioninclude CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)₃), andthe like. Non-limiting examples are disclosed in U.S. Pat. Nos.3,709,853, 3,709,954, 3,231,550, 3,242,099 and 4,077,904, which areherein fully incorporated by reference.

[0027] Still other conventional-type transition metal catalyst compoundsand catalyst systems suitable for use in the present invention aredisclosed in U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566, 4,376,062,4,379,758, 5,066,737, 5,763,723, 5,849,655, 5,852,144, 5,854,164 and5,869,585 and published EP-A2 0 416 815 A2 and EP-A1 0 420 436, whichare all herein incorporated by reference.

[0028] Other catalysts may include cationic catalysts such as AL^(C)l₃,and other cobalt, iron, nickel and palladium catalysts well known in theart. See for example U.S. Pat. Nos. 3,487,112, 4,472,559, 4,182,814 and4,689,437 all of which are incorporated herein by reference.

[0029] Typically, these conventional-type transition metal catalystcompounds excluding some conventional-type chromium catalyst compoundsare activated with one or more of the conventional-type cocatalystsdescribed below.

[0030] Conventional-Type Cocatalysts

[0031] Conventional-type cocatalyst compounds for the aboveconventional-type transition metal catalyst compounds may be representedby the formula M³M⁴ _(v)X² _(c)R³ _(b-c), wherein M³ is a metal fromGroup 1 to 3 and 12 to 13 of the Periodic Table of Elements; M⁴ is ametal of Group 1 of the Periodic Table of Elements; v is a number from 0to 1; each X² is any halogen; c is a number from 0 to 3; each R³ is amonovalent hydrocarbon radical or hydrogen; b is a number from 1 to 4;and wherein b minus c is at least 1. Other conventional-typeorganometallic cocatalyst compounds for the above conventional-typetransition metal catalysts have the formula M³R³k, where M³ is a GroupIA, IIA, IIB or IIIA metal, such as lithium, sodium, beryllium, barium,boron, aluminum, zinc, cadmium, and gallium; k equals 1, 2 or 3depending upon the valency of M³ which valency in turn normally dependsupon the particular Group to which M³ belongs; and each R³ may be anymonovalent radical that include hydrocarbon radicals and hydrocarbonradicals containing a Group 13 to 16 element like fluoride, aluminum oroxygen or a combination thereof.

[0032] Non-limiting examples of conventional-type organometalliccocatalyst compounds useful with the conventional-type catalystcompounds described above include methyllithium, butyllithium,dihexylmercury, butylmagnesium, diethyL^(C)admium, benzylpotassium,diethylzinc, tri-n-butylaluminum, diisobutyl ethylboron,diethyL^(C)admium, di-n-butylzinc and tri-n-amylboron, and, inparticular, the aluminum alkyls, such as tri-hexyl-aluminum,triethylaluminum, trimethylaluminum, and tri-isobutylaluminum. Otherconventional-type cocatalyst compounds include mono-organohalides andhydrides of Group 2 metals, and mono- or di-organohalides and hydridesof Group 3 and 13 metals. Non-limiting examples of suchconventional-type cocatalyst compounds include di-isobutylaluminumbromide, isobutylboron dichloride, methyl magnesium chloride,ethylberyllium chloride, ethyl calcium bromide, di-isobutylaluminumhydride, methyl cadmium hydride, diethylboron hydride,hexylberylliumhydride, dipropylboron hydride, octylmagnesium hydride,butylzinc hydride, dichloroboron hydride, di-bromo-aluminum hydride andbromocadmium hydride. Conventional-type organometallic cocatalystcompounds are known to those in the art and a more complete discussionof these compounds may be found in U.S. Pat. Nos. 3,221,002 and5,093,415, which are herein fully incorporated by reference.

[0033] Bulky Ligand Metallocene-Type Catalyst Compounds

[0034] Generally, bulky ligand metallocene-type catalyst compoundsinclude half and full sandwich compounds having one or more bulkyligands bonded to at least one metal atom. Typical bulky ligandmetallocene-type compounds are generally described as containing one ormore bulky ligand(s) and one or more leaving group(s) bonded to at leastone metal atom. In one preferred embodiment, at least one bulky ligandsis η-bonded to the metal atom, most preferably η⁵-bonded to the metalatom.

[0035] The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s), aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadiene, a cyclooctatetraendiyl or animide ligand. The metal atom is preferably selected from Groups 3through 15 and the lanthanide or actinide series of the Periodic Tableof Elements. Preferably the metal is a transition metal from Groups 4through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

[0036] In one embodiment, the bulky ligand metallocene-type catalystcompounds of the invention are represented by the formula:

L^(A)L^(B)MQ_(n)  (I)

[0037] where M is a metal atom from the Periodic Table of the Elementsand may be a Group 3 to 12 metal or from the lanthanide or actinideseries of the Periodic Table of Elements, preferably M is a Group 4, 5or 6 transition metal, more preferably M is a Group 4 transition metal,even more preferably M is zirconium, hafnium or titanium. The bulkyligands, L^(A) and L^(B), are open, acyclic or fused ring(s) or ringsystem(s) such as unsubstituted or substituted, cyclopentadienyl ligandsor cyclopentadienyl-type ligands, heteroatom substituted and/orheteroatom containing cyclopentadienyl-type ligands. Non-limitingexamples of bulky ligands include cyclopentadienyl ligands,cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands,fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiylligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoylligands, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands,borabenzene ligands and the like, including hydrogenated versionsthereof, for example tetrahydroindenyl ligands. In one embodiment, L^(A)and L^(B) may be any other ligand structure capable of η-bonding to M,preferably η³-bonding to M and most preferably η⁵-bonding . In yetanother embodiment, the atomic molecular weight (MW) of L^(A) or L^(B)exceeds 60 a.m.u., preferably greater than 65 a.m.u. In anotherembodiment, L^(A)and L^(B) may comprise one or more heteroatoms, forexample, nitrogen, silicon, boron, germanium, sulfur, oxygen andphosphorous, in combination with carbon atoms to form an open, acyclic,or preferably a fused, ring or ring system, for example, ahetero-cyclopentadienyl ancillary ligand. Other L^(A) and L^(B) bulkyligands include but are not limited to bulky amides, phosphides,alkoxides, aryloxides, imides, carbolides, borollides, porphyrins,phthalocyanines, corrins and other polyazomacrocycles. Independently,each L^(A) and L^(B) may be the same or different type of bulky ligandthat is bonded to M. In one embodiment of formula (I) only one of eitherL^(A) or L^(B) is present.

[0038] Independently, each L^(A) and L^(B) may be unsubstituted orsubstituted with a combination of substituent groups R. Non-limitingexamples of substituent groups R include one or more from the groupselected from hydrogen, or linear, branched alkyl radicals, or alkenylradicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylaminoradicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. In a preferred embodiment, substituent groups Rhave up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, thatcan also be substituted with halogens or heteroatoms or the like.Non-limiting examples of alkyl substituents R include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like. Other hydrocarbyl radicals includefluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl,chlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

[0039] Other ligands may be bonded to the metal M, such as at least oneleaving group Q. For the purposes of this patent specification andappended claims the term “leaving group” is any ligand that can beabstracted from a bulky ligand metallocene-type catalyst compound toform a bulky ligand metallocene-type catalyst cation capable ofpolymerizing one or more olefin(s). In one embodiment, Q is amonoanionic labile ligand having a sigma-bond to M.

[0040] Non-limiting examples of Q ligands include weak bases such asamines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicalshaving from 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike. Depending on the oxidation state of the metal, the value for n is0, 1 or 2 such that formula (I) above represents a neutral bulky ligandmetallocene-type catalyst compound.

[0041] In one embodiment, the bulky ligand metallocene-type catalystcompounds of the invention include those of formula (I) where L^(A) andL^(B) are bridged to each other by a bridging group, A, such that theformula is represented by

L^(A)AL^(B)MQ_(n)  (II)

[0042] These bridged compounds represented by formula (II) are known asbridged, bulky ligand metallocene-type catalyst compounds. L^(A), L^(B),M, Q and n are as defined above. Non-limiting examples of bridging groupA include bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, boron, germanium andtin atom or a combination thereof. Preferably bridging group A containsa carbon, silicon or germanium atom, most preferably A contains at leastone silicon atom or at least one carbon atom. The bridging group A mayalso contain substituent groups R as defined above including halogens.Non-limiting examples of bridging group A may be represented by R′₂C,R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ is independently, a radicalgroup which is hydride, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, hydrocarbyl-substitutedorganometalloid, halocarbyl-substituted organometalloid, disubstitutedboron, disubstituted pnictogen, substituted chalcogen, or halogen or twoor more R′ may be joined to form a ring or ring system.

[0043] In one embodiment, the bulky ligand metallocene-type catalystcompounds are those where the R substituents on the bulky ligands L^(A)and L^(B) of formulas (I) and (II) are substituted with the same ordifferent number of substituents on each of the bulky ligands. Inanother embodiment, the bulky ligands L^(A) and L^(B)of formulas (I) and(II) are different from each other.

[0044] Other bulky ligand metallocene-type catalyst compounds andcatalyst systems useful in the invention may include those described inU.S. Pat. Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022,5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401,5,723,398, 5,753,578, 5,854,363 and 5,856,547 5,858,903, 5,859,158 and5,929,266 and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO99/14221 and European publications EP-A-0 578 838, EP-A-0 638 595,EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819,EP-B1-0 748 821 and EP-B1-0 757 996, all of which are herein fullyincorporated by reference.

[0045] In one embodiment, bulky ligand metallocene-type catalystscompounds useful in the invention include bridged heteroatom, mono-bulkyligand metallocene-type compounds. These types of catalysts and catalystsystems are described in, for example, PCT publication WO 92/00333, WO94/07928, WO 91/04257, WO 94/03506, WO96/00244 and WO 97/15602 and U.S.Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and5,264,405 and European publication EP-A-0 420 436, all of which areherein fully incorporated by reference.

[0046] In this embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(C)AJMQ_(n)  (III)

[0047] where M is a Group 3 to 16 metal atom or a metal selected fromthe Group of actinides and lanthanides of the Periodic Table ofElements, preferably M is a Group 4 to 12 transition metal, and morepreferably M is a Group 4, 5 or 6 transition metal, and most preferablyM is a Group 4 transition metal in any oxidation state, especiallytitanium; L^(C) is a substituted or unsubstituted bulky ligand bonded toM; J is bonded to M; A is bonded to M and J; J is a heteroatom ancillaryligand; and A is a bridging group; Q is a univalent anionic ligand; andn is the integer 0,1 or 2. In formula (III) above, L^(C), A and J form afused ring system. In an embodiment, L^(C) of formula (III) is asdefined above for L^(A), A, M and Q of formula (III) are as definedabove in formula (I). In formula (III) J is a heteroatom containingligand in which J is an element with a coordination number of three fromGroup 15 or an element with a coordination number of two from Group 16of the Periodic Table of Elements. Preferably J contains a nitrogen,phosphorus, oxygen or sulfur atom with nitrogen being most preferred.

[0048] In another embodiment, the bulky ligand type metallocene-typecatalyst compound is a complex of a metal, preferably a transitionmetal, a bulky ligand, preferably a substituted or unsubstitutedpi-bonded ligand, and one or more heteroallyl moieties, such as thosedescribed in U.S. Pat. Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057,all of which are herein fully incorporated by reference.

[0049] In an embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(D)MQ₂(YZ)X_(n)  (IV)

[0050] where M is a Group 3 to 16 metal, preferably a Group 4 to 12transition metal, and most preferably a Group 4, 5 or 6 transitionmetal; LD is a bulky ligand that is bonded to M; each Q is independentlybonded to M and Q₂(YZ) forms a unicharged polydentate ligand; A or Q isa univalent anionic ligand also bonded to M; X is a univalent anionicgroup when n is 2 or X is a divalent anionic group when n is 1; n is 1or 2.

[0051] In formula (IV), L and M are as defined above for formula (I). Qis as defined above for formula (I), preferably Q is selected from thegroup consisting of —O—, —NR—, —CR₂—and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

[0052] In another embodiment of the invention, the bulky ligandmetallocene-type catalyst compounds are heterocyclic ligand complexeswhere the bulky ligands, the ring(s) or ring system(s), include one ormore heteroatoms or a combination thereof. Non-limiting examples ofheteroatoms include a Group 13 to 16 element, preferably nitrogen,boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examplesof these bulky ligand metallocene-type catalyst compounds are describedin WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874005 and U.S. Pat. No. 5,637,660, 5,539,124, 5,554,775, 5,756,611,5,233,049, 5,744,417, and 5,856,258 all of which are herein incorporatedby reference.

[0053] In another embodiment, the bulky ligand metallocene-type catalystcompounds are those complexes known as transition metal catalysts basedon bidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference. In another embodiment,the bulky ligand metallocene-type catalyst compounds are those describedin PCT publications WO 99/01481 and WO 98/42664, which are fullyincorporated herein by reference.

[0054] In one embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

((Z)XA_(t)(YJ))_(q)MQ_(n)  (V)

[0055] where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X, Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional. In another embodiment, where X is nitrogen orphosphorous then Z is present. In an embodiment, Z is preferably an arylgroup, more preferably a substituted aryl group.

[0056] Other Bulky Ligand Metallocene-Type Catalyst Compounds

[0057] It is within the scope of this invention, in one embodiment, thatthe bulky ligand metallocene-type catalyst compounds include complexesof Ni²⁺ and Pd²⁺ described in the articles Johnson, et al., “New Pd(II)-and Ni(II)-Based Catalysts for Polymerization of Ethylene anda-Olefins”, J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson, et al.,“Copolymerization of Ethylene and Propylene with Functionalized VinylMonomers by Palladium(II) Catalysts”, J. Am. Chem. Soc., 1996, 118,267-268, and WO 96/23010 published Aug. 1, 1996, WO 99/02472, U.S. Pat.Nos. 5,852,145, 5,866,663 and 5,880,241, which are all herein fullyincorporated by reference. These complexes can be either dialkyl etheradducts, or alkylated reaction products of the described dihalidecomplexes that can be activated to a cationic state by the activators ofthis invention described below.

[0058] Also included as bulky ligand metallocene-type catalyst are thosediimine based ligands of Group 8 to 10 metal compounds disclosed in PCTpublications WO 96/23010 and WO 97/48735 and Gibson, et. al., Chem.Comm., pp. 849-850 (1998), all of which are herein incorporated byreference.

[0059] Other bulky ligand metallocene-type catalysts are those Group 5and 6 metal imido complexes described in EP-A2-0 816 384 and U.S. Pat.No. 5,851,945, which is incorporated herein by reference. In addition,bulky ligand metallocene-type catalysts include bridged bis(arylamido)Group 4 compounds described by D. H. McConville, et al., inOrganometallics 1195, 14, 5478-5480, which is herein incorporated byreference. Other bulky ligand metallocene-type catalysts are describedas bis(hydroxy aromatic nitrogen ligands) in U.S. Pat. No. 5,852,146,which is incorporated herein by reference. Other metallocene-typecatalysts containing one or more Group 15 atoms include those describedin WO 98/46651, which is herein incorporated herein by reference.

[0060] It is also contemplated that in one embodiment, the bulky ligandmetallocene-type catalysts of the invention described above includetheir structural or optical or enantiomeric isomers (meso and racemicisomers, for example see U.S. Pat. No. 5,852,143, incorporated herein byreference) and mixtures thereof.

[0061] Activator and Activation Methods for the Bulky LigandMetallocene-Type Catalyst Compounds

[0062] The above described bulky ligand metallocene-type catalystcompounds are typically activated in various ways to yield catalystcompounds having a vacant coordination site that will coordinate,insert, and polymerize olefin(s), an activated polymerization catalyst.

[0063] For the purposes of this patent specification and appendedclaims, the term “activator” is defined to be any compound or componentor method which can activate any of the bulky ligand metallocene-typecatalyst compounds of the invention as described above. Non-limitingactivators, for example may include a Bronsted acid or anon-coordinating ionic activator or ionizing activator or any othercompound including Bronsted bases, aluminum alkyls, conventional-typecocatalysts and combinations thereof that can convert a neutral bulkyligand metallocene-type catalyst compound to a catalytically activebulky ligand metallocene cation. It is within the scope of thisinvention to use alumoxane or modified alumoxane as an activator, and/orto also use ionizing activators, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983) or combinationthereof, that would ionize the neutral bulky ligand metallocene-typecatalyst compound.

[0064] In one embodiment, an activation method using ionizing ioniccompounds not containing an active proton but capable of producing botha bulky ligand metallocene-type catalyst cation and a non-coordinatinganion are also contemplated, and are described in EP-A-0 426 637, EP-A-0573 403 and U.S. Pat. No. 5,387,568, which are all herein incorporatedby reference.

[0065] There are a variety of methods for preparing alumoxane andmodified alumoxanes, non-limiting examples of which are described inU.S. Pat. No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529,5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166 and5,856,256 and European publications EP-A-0 561 476, EP-B1-0 279 586,EP-A-0 594-218 and EP-B1-0 586 665, and PCT publication WO 94/10180, allof which are herein fully incorporated by reference.

[0066] Organoaluminum compounds useful as activators includetriethylaluminum, triisobutylaluminum, trimethylaluminum, tri-n-hexylaluminum and the like.

[0067] Ionizing compounds may contain an active proton, or some othercation associated with but not coordinated to or only looselycoordinated to the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

[0068] Other activators include those described in PCT publication WO98/07515 such as tris (2, 2′, 2″ -nonafluorobiphenyl) fluoroaluminate,which publication is fully incorporated herein by reference.Combinations of activators are also contemplated by the invention, forexample, alumoxanes and ionizing activators in combinations, see forexample, EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044and U.S. Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference. Other activators include aluminum/boroncomplexes as described in EP 608 830 B1, which is herein incorporated byreference. WO 98/09996 incorporated herein by reference describesactivating bulky ligand metallocene-type catalyst compounds withperchlorates, periodates and iodates including their hydrates. WO98/30602 and WO 98/30603 incorporated by reference describe the use oflithium (2,2′-bisphenyl-ditrimethylsilicate)·4THF as an activator for abulky ligand metallocene-type catalyst compound. EP-B1-0 781 299describes using a silylium salt in combination with a non-coordinatingcompatible anion. Also, methods of activation such as using radiation(see EP-B1-0 615 981 herein incorporated by reference), electrochemicaloxidation, and the like are also contemplated as activating methods forthe purposes of rendering the neutral bulky ligand metallocene-typecatalyst compound or precursor to a bulky ligand metallocene-type cationcapable of polymerizing olefins. Other activators or methods foractivating a bulky ligand metallocene-type catalyst compound aredescribed in for example, U.S. Pat. Nos. 5,849,852, 5,859,653 and5,869,723 and PCT WO 98/32775, which are herein incorporated byreference.

[0069] It is also within the scope of this invention that the abovedescribed bulky ligand metallocene-type catalyst compounds can becombined with one or more of the catalyst compounds represented byformulas (I) through (V) with one or more activators or activationmethods described above.

[0070] It is further contemplated by the invention that other catalystscan be combined with the bulky ligand metallocene-type catalystcompounds of the invention. For example, see U.S. Pat. Nos. 4,937,299,4,935,474, 5,281,679, 5,359,015, 5,470,811, and 5,719,241 all of whichare herein fully incorporated herein reference. It is also contemplatedthat any one of the bulky ligand metallocene-type catalyst compounds ofthe invention have at least one fluoride or fluorine containing leavinggroup as described in U.S. application Ser. No. 09/191,916 filed Nov.13, 1998.

[0071] In another embodiment of the invention one or more bulky ligandmetallocene-type catalyst compounds or catalyst systems may be used incombination with one or more conventional-type catalyst compounds orcatalyst systems. Non-limiting examples of mixed catalysts and catalystsystems are described in U.S. Pat. Nos. 4,159,965, 4,325,837, 4,701,432,5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264,5,723,399 and 5,767,031 and PCT Publication WO 96/23010 published Aug.1, 1996, all of which are herein fully incorporated by reference.Supports, Carriers and General Supporting Techniques

[0072] The above described conventional-type transition metal catalystcompounds and catalyst systems and bulky ligand metallocene-typecatalyst compounds and catalyst systems may be combined with one or moresupport materials or carriers using one of the support methods wellknown in the art or as described below. For example, in a most preferredembodiment, a bulky ligand metallocene-type catalyst compound orcatalyst system is in a supported form, for example deposited on,contacted with, vapourized with, bonded to, or incorporated within,adsorbed or absorbed in, or on, a support or carrier.

[0073] The terms “support” or “carrier” are used interchangeably and areany support material, preferably a porous support material, morepreferably an inorganic support or an organic support. Inorganicsupports are preferred for example inorganic oxides and inorganicchlorides. Other carriers include resinous support materials such aspolystyrene, functionalized or crosslinked organic supports, such aspolystyrene divinyl benzene polyolefins or polymeric compounds,zeolites, clays, talc, or any other organic or inorganic supportmaterial and the like, or mixtures thereof. The most preferred carriersare inorganic oxides that include those Group 2, 3, 4, 5, 13 or 14 metaloxides. The preferred supports include silica, alumina, silica-alumina,magnesium chloride, and mixtures thereof.

[0074] Other useful supports include magnesia, titania, zirconia,montmorillonite (EP-B1 0 511 665) and the like. Also, combinations ofthese support materials may be used, for example, silica-chromium,silica-alumina, silica-titania and the like.

[0075] It is preferred that the carrier, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the carrier is in the range of fromabout 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5cc/g and average particle size of from about 10 to about 200 μm. Mostpreferably the surface area of the carrier is in the range is from about100 to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g andaverage particle size is from about 5 to about 100 μm. The average poresize of the carrier of the invention typically has pore size in therange of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 350 Å.

[0076] Examples of supporting the bulky ligand metallocene-type catalystsystems of the invention are described in U.S. Pat. Nos. 4,701,432,4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892,5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766,5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835, 5,625,015,5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400, 5,723,402,5,731,261, 5,759,940, 5,767,032, 5,770,664 and 5,846,895 and U.S.application Ser. No. 271,598 filed Jul. 7, 1994 and U.S. application SerNo. 788,736 filed Jan. 23, 1997 and PCT publications WO 95/32995, WO95/14044, WO 96/06187 and WO 97/02297, and EP-B1-0 685 494 all of whichare herein fully incorporated by reference. Examples of supportingconventional-type transition metal catalyst compounds are also wellknown in the art.

[0077] There are various other methods in the art for supporting apolymerization catalyst compound or catalyst system of the invention.For example, the bulky ligand metallocene-type catalyst compound of theinvention may contain a polymer bound ligand as described in U.S. Pat.Nos. 5,473,202 and 5,770,755, which is herein fully incorporated byreference; the bulky ligand metallocene-type catalyst system of theinvention may be spray dried as described in U.S. Pat. No. 5,648,310,which is herein fully incorporated by reference; the support used withthe bulky ligand metallocene-type catalyst system of the invention isfunctionalized as described in European publication EP-A-0 802 203,which is herein fully incorporated by reference, or at least onesubstituent or leaving group is selected as described in U.S. Pat. No.5,688,880, which is herein fully incorporated by reference.

[0078] In a preferred embodiment, the invention provides for a supportedbulky ligand metallocene-type catalyst system that includes anantistatic agent or surface modifier that is used in the preparation ofthe supported catalyst system as described in PCT publication WO96/11960, which is herein fully incorporated by reference. The catalystsystems of the invention can be prepared in the presence of an olefin,for example hexene-1.

[0079] In another embodiment, the bulky ligand metallocene-type catalystsystem can be combined with a carboxylic acid salt of a metal ester, forexample aluminum carboxylates such as aluminum mono, di- andtri-stearates, aluminum octoates, oleates and cyclohexylbutyrates, asdescribed in U.S. application Ser. No. 09/113,216, filed Jul. 10, 1998.

[0080] A preferred method for producing the supported bulky ligandmetallocene-type catalyst system of the invention is described below andis described in U.S. application Ser. Nos. 265,533, filed Jun. 24, 1994and 265,532, filed Jun. 24, 1994 and PCT publications WO 96/00245 and WO96/00243 both published Jan. 4, 1996, all of which are herein fullyincorporated by reference. In this preferred method, the bulky ligandmetallocene-type catalyst compound is slurried in a liquid to form ametallocene solution and a separate solution is formed containing anactivator and a liquid. The liquid may be any compatible solvent orother liquid capable of forming a solution or the like with the bulkyligand metallocene-type catalyst compounds and/or activator of theinvention. In the most preferred embodiment the liquid is a cyclicaliphatic or aromatic hydrocarbon, most preferably toluene. The bulkyligand metallocene-type catalyst compound and activator solutions aremixed together and added to a porous support or the porous support isadded to the solutions such that the total volume of the bulky ligandmetallocene-type catalyst compound solution and the activator solutionor the bulky ligand metallocene-type catalyst compound and activatorsolution is less than four times the pore volume of the porous support,more preferably less than three times, even more preferably less thantwo times; preferred ranges being from 1.1 times to 3.5 times range andmost preferably in the 1.2 to 3 times range.

[0081] Procedures for measuring the total pore volume of a poroussupport are well known in the art. Details of one of these procedures isdiscussed in Volume 1, Experimental Methods in Catalytic Research(Academic Press, 1968) (specifically see pages 67-96). This preferredprocedure involves the use of a classical BET apparatus for nitrogenabsorption. Another method well known in the art is described in Innes,Total Porosity and Particle Density of Fluid Catalysts By LiquidTitration, Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1956).

[0082] The mole ratio of the metal of the activator component to themetal of the supported bulky ligand metallocene-type catalyst compoundsare in the range of between 0.3:1 to 1000:1, preferably 20:1 to 800:1,and most preferably 50:1 to 500:1. Where the activator is an ionizingactivator such as those based on the aniontetrakis(pentafluorophenyl)boron, the mole ratio of the metal of theactivator component to the metal component of the bulky ligandmetallocene-type catalyst is preferably in the range of between 0.3:1 to3:1.

[0083] In one embodiment of the invention, olefin(s), preferably C₂ toC₃₀ olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of theconventional-type transition metal catalyst system and/or a bulky ligandmetallocene-type catalyst system of the invention prior to the mainpolymerization. The prepolymerization can be carried out batchwise orcontinuously in gas, solution or slurry phase including at elevatedpressures. The prepolymerization can take place with any olefin monomeror combination and/or in the presence of any molecular weightcontrolling agent such as hydrogen. For examples of prepolymerizationprocedures, see U.S. Pat. Nos. 4,748,221, 4,789,359, 4,923,833,4,921,825, 5,283,278 and 5,705,578 and European publication EP-B-0279863 and PCT Publication WO 97/44371 all of which are herein fullyincorporated by reference. In this embodiment, the prepolymerization ofolefin(s) takes place either in the presence of the solid compound,preferably a solid acid compound, or the solid compound is added afterthe prepolymerization, but prior to the main polymerization, or simplyadded to the reactor with an already formed prepolymerized catalyst or acombination thereof. For the purposes of this patent specification andappended claims only, prepolymerization is considered a method forimmobilizing a catalyst system and therefore considered to form asupported catalyst system.

[0084] In the most preferred embodiment, the solid compound, preferablythe solid acid compound is contacted with a preformed supportedpolymerization catalyst.

[0085] Compounds

[0086] There are various compounds that can be used to control thekinetics of an olefin polymerization catalyst. In the preferredembodiment, the invention relates to the use of a substantially solidcompound, preferably a solid compound that in the presence of apolymerization catalyst undergoes a phase change at a specifiedtemperature during a polymerization process to produce a substantiallyliquid compound, preferably a liquid compound. In one embodiment, thesolid compound has a weight loss of no greater than 20 weight percent,preferably less than 10 weight percent, more preferably less than 5weight percent, even more preferably less than 2 weight percent and mostpreferably less than 1 weight percent measured using a standardthermogravimetric analysis (TGA) at 80° C. for 20 minutes. In anotherembodiment of the invention the solid compound has a dielectric constantgreater than 2, preferably greater than 5, more preferably greater than10 and/or a melting temperature in the range of from 0° C. to 200° C.,preferably from 10° C. to 180° C., more preferably from 40° C. to 150°C., and most preferably from 80° C. to 130° C. The most preferredcompound is an acid, specifically a solid Bronsted acid.

[0087] Acid Compounds

[0088] It is preferred that the solid compound is an acid compound,preferably Bronsted acid, that when combined or contacted with thepolymerization catalyst prior to its introduction to a polymerizationprocess is essentially or completely unreactive with the polymerizationcatalyst. However, when the polymerization catalyst and solid compoundenter a polymerization environment, the solid component becomes a liquidat a temperature above the polymerization temperature that inactivatesthe polymerization catalyst. For purposes of this patent specificationand appended claims the terms “polymerization temperature” and “reactortemperature” are interchangeable. The conditions for the solid/liquidphase change depend on for example, the particular polymerizationprocess and/or the delivery mechanism for their introduction to apolymerization reactor.

[0089] The acid compounds may be represented by the following generalformula:

X—H,

[0090] where X—H is an acid, preferably a Bronsted acid (Bronsted, J. N.Rec. Trav. Chim. 1923, 42, 718), with a pKa of less than 20, preferablyless than 15, more preferably less than 10, most preferred less than 5.Some classes of Bronsted acids include ketones, alcohols, ammoniumsalts, nitrites, nitro compounds, acetylenes, phenols, carboxylic acidsand mineral acids. Examples of these classes include acetophenone,adamantanol, anilinium chloride, diphenyl-acetonitrile, picrolonic acid,phenylacetylene, phenol, benzoic acid and tungstic acid. Most preferredare carboxylic acids, including o-toluic acid, tropic acid,4-octyloxybenzoic acid, 4-bromophenylacetic acid, 2-phenoxybenzoic acid,3,4,5-triethoxybenzoic acid and 2,4-dimethoxybenzoic acid.

[0091] Especially preferred are acids having a high density offunctional groups, such as malic acid and glutaric acid.

[0092] Non-limiting examples of acid compounds include 3-methyladipicacid, DL-malic acid, tropic acid, glutaric acid, ketoglutaric acid,pimelic acid, mandelic acid, 3-t-butyladipic acid and L-malic acid. Itis most preferred that the acids of the invention are in a solid formhaving little to no vapour pressure.

[0093] The conditions at which the solid acid compound for example isproduced may be controlled by varying the acid compound used. This maybe done by choosing the melting temperature of the acid compound. In oneembodiment, the acid compound has a melting point in the range of from50° C. to about 130° C., preferably in the range of from about 60° C. toabout 120° C., more preferably in the range of from 70° C. to about 110° C., and most preferably in the range of from 80° C. to about 105° C.

[0094] In another embodiment, the acid compound has a melting pointgreater than 60° C., preferably greater than 70° C., more preferablygreater than 75° C., and most preferably greater than 80° C.

[0095] In one embodiment, the acid compound melts at a temperaturegreater than 5° C. above the polymerization temperature.

[0096] In one preferred embodiment, the acid is selected from one ormore of the group consisting of tropic acid, glutaric acid, methyladipic acid, L-malic acid, 4-octyloxybenzoic acid, 3-t-butyladipic acid,ketoglutaric acid, tropic acid and DL-malic acid.

[0097] In an embodiment, more than one solid compound, preferably morethan one acid compound is used. In this way the kinetics of thepolymerization catalyst can be controlled at two different temperatureconditions for example.

[0098] Insolubility in hydrocarbons is indispensable for slurry andsolution phase reactions. If desired, a second component (adjuvant) canbe added that facilitates the phase change of the solid acid to itsliquid or substantially liquid form.

[0099] In an embodiment, the acid has a melting point such that the acidis solid in the temperature range of from 25° C. to normal reactionconditions of temperature in the reactor during polymerization. Normalpolymerization temperatures vary depending on the process used and/orthe polymer produced. Typically polymerization temperatures in a gasphase process are in the range of 50° C. to about 120° C., morepreferably from about 60° C. to about 110° C., most preferably fromabout 65° C. to about 100° C. Other polymerization temperatures arediscussed later in this patent specification.

[0100] The most preferred acid compounds are polar acid compounds,generally include di- and tri-acids having a very low vapour pressure, alow hydrocarbon solubility, preferably no vapor pressure. Also preferredare acid compounds that have a low toxicity.

[0101] Other preferred properties for the acid compounds include thefollowing considerations: 1) tunable so that its phase changetemperature can be customized for a given process; 2) low toxicity; 3)not volatile as a solid; 4) responds quickly over a narrow temperaturerange; 5) quickly undergoes a phase change from solid to liquid; 6)unaffected by the type of catalyst; 7) operates under various reactorconditions; 8) evenly distributed throughout the reactor, and preferablydoes not enter the recycle line; 9) not significantly affect thepelletizing process; 10) not adversely affect downstream polymerproperties; and 11) easily handled.

[0102] In a preferred embodiment, the acid is a polar compound where theacid compound has at least one —OH functionality. Most preferably thesepolar compounds are insoluble in aliphatic hydrocarbons. The mostpreferred acid is L-malic acid.

[0103] Methods for Using the Combination of Compounds

[0104] The use of the solid compound, preferably the solid acidcompounds of the invention can vary. For example, the acid compound canbe added or introduced with or without a polymerization catalystdirectly to a polymerization process. The acid compound may be addedseparately and/or simultaneously to the reactor with a polymerizationcatalyst, preferably a supported polymerization catalyst. In anembodiment, the acid compound is contacted with a catalyst compoundprior to being introduced to the reactor. Other embodiments may includeplacing the acid compound on a support material and then introducing thesupport material to the polymerization reactor.

[0105] The solid acid compound may be introduced in one embodiment inthe recycle stream of a gas phase polymerization process or below thedistributor plate or in a region within the reactor where the tendencyfor sheeting to occur is high. The details of a gas phase polymerizationprocess is discussed later in this patent specification.

[0106] In yet another embodiment, the solid compound, preferably thesolid acid compound, is used in combination with an unsupported catalystsystem or even as a supported for a catalyst system.

[0107] In the most preferred embodiment, the acid compound is used witha supported catalyst system. A most preferred method for making asupported catalyst system of the invention generally involves thecombining, contacting, blending, bonding and/or mixing any of the abovedescribed catalyst compounds, preferably a bulky ligand metallocene-typecatalyst compound using any of the techniques previously described.

[0108] In one embodiment of the method of the invention, a catalystcompound is combined, contacted, bonded, blended, and/or mixed with anacid compound. In a most preferred embodiment, the catalyst compound isa conventional-type transition metal catalyst and/or a bulky ligandmetallocene-type catalyst supported on a carrier. In one embodiment, theacid compound is in a mineral oil slurry with or without a catalystsystem, preferably with a supported catalyst system that is introducedto a polymerization process.

[0109] In another embodiment, the steps of the method of the inventioninclude forming a polymerization catalyst, preferably forming asupported polymerization catalyst, and contacting the polymerizationcatalyst, preferably the supported polymerization catalyst, with apolar, solid compound, preferably an acid. In a preferred method, thepolymerization catalyst comprises a catalyst compound, an activator anda carrier, preferably the polymerization catalyst is a supported bulkyligand metallocene-type catalyst.

[0110] In one embodiment of the method of the invention the acidcompound is contacted with the catalyst system, preferably a supportedcatalyst system, most preferably a supported bulky ligandmetallocene-type catalyst system under ambient temperatures andpressures. Preferably the contact temperature for combining thepolymerization catalyst and the acid compound is in the range of from 0°C. to about 100° C., more preferably from 15° C. to about 75° C., mostpreferably at about ambient temperature and pressure.

[0111] In a preferred embodiment, the contacting of the polymerizationcatalyst and the solid, polar compound, preferably the acid compound isperformed under an inert gaseous atmosphere, such as nitrogen. However,it is contemplated that the combination of the polymerization catalystand the acid compound may be performed in the presence of olefin(s),solvents, hydrogen and the like.

[0112] In one embodiment, the acid may be added at any stage during thepreparation of a catalyst composition so long as the solid acid does notreact with the composition during its preparation.

[0113] In one embodiment of the method of the invention, thepolymerization catalyst and the acid compound is combined in thepresence of a liquid, for example the liquid may be a mineral oil,toluene, hexane, isobutane or a mixture thereof. In a more preferredmethod the acid compound is combined with a polymerization catalyst thathas been formed in a liquid, preferably in a slurry, or combined with asubstantially dry or dried, polymerization catalyst that has been placedin a liquid and reslurried.

[0114] Preferably, prior to use, the polymerization catalyst iscontacted with the acid compound for a period of time greater than asecond, preferably from about 1 minute to about 48 hours, morepreferably from about 10 minutes to about 10 hours, and most preferablyfrom about 30 minutes to about 6 hours. The period of contacting refersto the mixing time only.

[0115] In an embodiment, the mole ratio of the solid polar compound,preferably the solid acid compound, to the metal of the polymerizationcatalyst is the range from 5000 to about 0.2, preferably from about 1000to about 0.5, more preferably from about 500 to about 1, and mostpreferably from about 250 to about 10.

[0116] In another embodiment, the weight ratio of the solid polarcompound, preferably the solid acid compound, to the weight of thepolymerization catalyst (including support if a supported polymerizationcatalyst) is the range from 100 to 0.001, preferably from about 10 toabout 0.01, more preferably from 5 to 0.1, and most preferably from 2 toabout 0.2.

[0117] Mixing techniques and equipment contemplated for use in themethod of the invention are well known. Mixing techniques may involveany mechanical mixing means, for example shaking, stirring, tumbling,and rolling. Another technique contemplated involves the use offluidization, for example in a fluid bed reactor vessel where circulatedgases provide the mixing. Non-limiting examples of mixing equipment forcombining, a solid polymerization catalyst and the acid compoundsinclude a ribbon blender, a static mixer, a double cone blender, a drumtumbler, a drum roller, a dehydrator, a fluidized bed, a helical mixerand a conical screw mixer.

[0118] In a preferred embodiment of the invention the catalyst system ofthe invention is supported on a carrier, preferably the supportedcatalyst system is substantially dried, preformed, substantially dryand/or free flowing. In an especially preferred method of the invention,the preformed supported catalyst system is contacted with a solid polarcompound, preferably a solid acid compound. The acid compound may be insolution or slurry or in a dry state, preferably the acid compound is ina substantially dry or dried state. If the acid is in solution, the acidremains substantially in a solid state.

[0119] In an embodiment, the method of the invention provides forco-injecting an unsupported polymerization catalyst and a solid polarcompound, preferably a solid acid compound into the reactor. In oneembodiment the polymerization catalyst is used in the unsupported form,preferably in a liquid form such as described in U.S. Pat. Nos.5,317,036 and 5,693,727 and European publication EP-A-0 593 083, all ofwhich are herein incorporated by reference. The polymerization catalystin liquid form can be fed with a solid polar compound, preferably asolid acid compound together or separately to a reactor using theinjection methods described in PCT publication WO 97/46599, which isfully incorporated herein by reference. Where an unsupported bulkyligand metallocene-type catalyst system is used the mole ratio of themetal of the activator component to the metal of the bulky ligandmetallocene-type catalyst compound is in the range of between 0.3:1 to10,000:1, preferably 100:1 to 5000:1, and most preferably 500:1 to2000:1.

[0120] In one embodiment, the polymerization catalyst has a productivitygreater than 1500 grams of polymer per gram of catalyst, preferablygreater than 2000 grams of polymer per gram of catalyst, more preferablygreater than 2500 grams of polymer per gram of catalyst and mostpreferably greater than 3000 grams of polymer per gram of catalyst. Inone embodiment, when the solid polar compound, preferably the solid acidcompound of the invention undergoes a phase change, the polymerizationcatalyst productivity is reduced to less than 1500 grams of polymer pergram of catalyst, preferably less than 1000 grams of polymer per gram ofcatalyst, more preferably less than 500 grams of polymer per gram ofcatalyst, even more preferably less than 100 grams of polymer per gramof catalyst, and still even more preferably less than 25 grams ofpolymer per gram of catalyst and most preferably to less than ismeasurably possible or 0 grams of polymer per gram of catalyst.

[0121] In one embodiment, a binder is used to hold the solid polarcompound, preferably the solid acid compound to the catalyst, or simplyto facilitate the phase change from a solid to a liquid or gas,preferably a liquid. The binder may be added to the catalyst in anynumber of ways, for instance the binder can be added just after thecatalyst is made and is still in a slurry state or prior to evaporationof any liquid in which the catalyst was prepared. If a binder isutilized it is preferable to add it to the dried preformed supportedpolymerization catalyst. Non-limiting examples of binders includepolyethylene oxide, polyethylene/propylene oxide, mineral oil, silica,alumina, silicone oil, various waxes such as camauba wax, surfactantssuch as sodium dodecylbenzene sulfonate and chelating agents such asEDTA.

[0122] The solid polar compound, preferably the solid acid compound, inconjunction with a supported polymerization catalyst may be combinedwith agents that would help dissipate static charge build up and/ormodify the flow properties of the material and/or improve free flow ofpowders by reducing powder bed packing, decreasing particle coherence,and reducing interparticle friction. Non-limiting examples of theseagents include silica such as cabosil, clays, surfactants such as estersof fatty acids, metal salts of fatty acids, silica, metal halides,solvated metal halides, amines, polyoxyethylene and polyoxypropylene andtheir derivatives, and sulfonates.

[0123] Polymerization Process

[0124] The catalyst compositions including the solid compound,preferably the solid acid compound of the invention described above aresuitable for use in any prepolymerization and/or polymerization processover a wide range of temperatures and pressures. The temperatures may bein the range of from −60° C. to about 280° C., preferably from 50° C. toabout 200° C., and the pressures employed may be in the range from 1atmosphere to about 500 atmospheres or higher.

[0125] Polymerization processes include solution, gas phase, slurryphase and a high pressure process or a combination thereof. Particularlypreferred is a gas phase or slurry phase polymerization of one or moreolefins at least one of which is ethylene or propylene.

[0126] In one embodiment, the process of this invention is directedtoward a solution, high pressure, slurry or gas phase polymerizationprocess of one or more olefin monomers having from 2 to 30 carbon atoms,preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbonatoms. The invention is particularly well suited to the polymerizationof two or more olefin monomers of ethylene, propylene, butene-1,pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

[0127] Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

[0128] In the most preferred embodiment of the process of the invention,a copolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process.

[0129] In another embodiment of the process of the invention, ethyleneor propylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

[0130] In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms. Polypropylene polymers may be produced using the particularlybridged bulky ligand metallocene-type catalysts as described in U.S.Pat. Nos. 5,296,434 and 5,278,264, both of which are herein incorporatedby reference.

[0131] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228, all of which are fully incorporated herein byreference.)

[0132] The reactor pressure in a gas phase process may vary from about100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the rangeof from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), morepreferably in the range of from about 250 psig (1724 kPa) to about 350psig (2414 kPa).

[0133] The reactor temperature in a gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 70° C. to 1 10C, andmost preferably in the range of from about 70° C. to about 95° C.

[0134] Other gas phase processes contemplated by the process of theinvention include series or multistage polymerization processes. Alsogas phase processes contemplated by the invention include thosedescribed in U.S. Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, andEuropean publications EP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

[0135] In a preferred embodiment, the reactor utilized in the presentinvention is capable and the process of the invention is producinggreater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr),still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), stilleven more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and mostpreferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than100,000 lbs/hr (45,500 Kg/hr).

[0136] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0137] A preferred polymerization technique of the invention is referredto as a particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484, which isherein fully incorporated by reference.

[0138] In an embodiment the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

[0139] Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998 and 5,589,555, which are fullyincorporated herein by reference.

[0140] A preferred process of the invention is where the process,preferably a slurry or gas phase process is operated in the presence ofa bulky ligand metallocene-type catalyst system of the invention and inthe absence of or essentially free of any scavengers, such astriethylaluminum, trimethylaluminum, tri-isobutylaluminum andtri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and thelike. This preferred process is described in PCT publication WO 96/08520and U.S. Pat. No. 5,712,352 and 5,763,543, which are herein fullyincorporated by reference.

[0141] Polymer Product of the Invention

[0142] The polymers produced by the process of the invention can be usedin a wide variety of products and end-use applications. The polymersproduced by the process of the invention include linear low densitypolyethylene, elastomers, plastomers, high density polyethylenes, lowdensity polyethylenes, polypropylene and polypropylene copolymers.

[0143] The polymers, typically ethylene based polymers, have a densityin the range of from 0.86g/cc to 0.97 g/cc, preferably in the range offrom 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/ccto 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.Density is measured in accordance with ASTM-D-1238.

[0144] The polymers produced by the process of the invention typicallyhave a molecular weight distribution, a weight average molecular weightto number average molecular weight (M_(w)/M_(n)) of greater than 1.5 toabout 30, particularly greater than 2 to about 10, more preferablygreater than about 2.2 to less than about 8, and most preferably from2.5 to 8.

[0145] Also, the polymers of the invention typically have a narrowcomposition distribution as measured by Composition Distribution BreadthIndex (CDBI). Further details of determining the CDBI of a copolymer areknown to those skilled in the art. See, for example, PCT PatentApplication WO 93/03093, published Feb. 18, 1993, which is fullyincorporated herein by reference.

[0146] The bulky ligand metallocene-type catalyzed polymers of theinvention in one embodiment have CDBI's generally in the range ofgreater than 50% to 100%, preferably 99%, preferably in the range of 55%to 85%, and more preferably 60% to 80%, even more preferably greaterthan 60%, still even more preferably greater than 65%.

[0147] In another embodiment, polymers produced using a bulky ligandmetallocene-type catalyst system of the invention have a CDBI less than50%, more preferably less than 40%, and most preferably less than 30%.

[0148] The polymers of the present invention in one embodiment have amelt index (MI) or (I₂) as measured by ASTM-D-1238-E in the range from0.01 dg/min to 1000 dg/min, more preferably from about 0.01 dg/min toabout 100 dg/min, even more preferably from about 0.1 dg/min to about 50dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.

[0149] The polymers of the invention in an embodiment have a melt indexratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from 10 to lessthan 25, more preferably from about 15 to less than 25.

[0150] The polymers of the invention in a preferred embodiment have amelt index ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 25, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65. In an embodiment, the polymer ofthe invention may have a narrow molecular weight distribution and abroad composition distribution or vice-versa, and may be those polymersdescribed in U.S. Pat. No. 5,798,427 incorporated herein by reference.

[0151] In yet another embodiment, propylene based polymers are producedin the process of the invention. These polymers include atacticpolypropylene, isotactic polypropylene, hemi-isotactic and syndiotacticpolypropylene. Other propylene polymers include propylene block orimpact copolymers. Propylene polymers of these types are well known inthe art see for example U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851,5,036,034 and 5,459,117, all of which are herein incorporated byreference.

[0152] The polymers of the invention may be blended and/or coextrudedwith any other polymer. Non-limiting examples of other polymers includelinear low density polyethylenes produced via conventional Ziegler-Nattaand/or bulky ligand metallocene-type catalysis, elastomers, plastomers,high pressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

[0153] Polymers produced by the process of the invention and blendsthereof are useful in such forming operations as film, sheet, and fiberextrusion and co-extrusion as well as blow molding, injection moldingand rotary molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc. in food-contact and non-food contactapplications. Fibers include melt spinning, solution spinning and meltblown fiber operations for use in woven or non-woven form to makefilters, diaper fabrics, medical garments, geotextiles, etc. Extrudedarticles include medical tubing, wire and cable coatings, geomembranes,and pond liners. Molded articles include single and multi-layeredconstructions in the form of bottles, tanks, large hollow articles,rigid food containers and toys, etc.

EXAMPLES

[0154] In order to provide a better understanding of the presentinvention including representative advantages thereof, the followingexamples are offered.

[0155] Catalyst

[0156] The polymerization catalyst used in the examples below wasprepared similarly to the following preparation. The bridged, bulkyligand metallocene-type catalyst compound wasdimethylsilyl-bis(tetrahydroindenyl)zirconium dichloride(Me₂Si(H₄Ind)₂ZrCl₂) available from Albemarle Corporation, Baton Rouge,La. The (Me₂Si(H₄Ind)₂ZrCl₂) catalyst compound was supported onCrosfield ES-70 grade silica dehydrated at 600° C. having approximately1.0 weight percent water Loss on Ignition (LOI). LOI is measured bydetermining the weight loss of the support material which has beenheated and held at a temperature of about 1000° C. for about 22 hours.The Crosfield ES-70 grade silica has an average particle size of 40microns and is available from Crosfield Limited, Warrington, England.

[0157] The first step in the manufacture of the supported bulky ligandmetallocene-type catalyst above involves forming a precursor solution.460 lbs (209 kg) of sparged and dried toluene is added to an agitatedreactor after which 1060 lbs (482 kg) of a 30 weight percentmethylaluminoxane (MAO) in toluene (available from Albemarle, BatonRouge, La.) is added. 947 lbs (430 kg) of a 2 weight percent toluenesolution of a dimethylsilyl-bis(tetrahydroindenyl) zirconium dichloridecatalyst compound and 600 lbs (272 kg) of additional toluene areintroduced into the reactor. The precursor solution is then stirred at80° F. to 100° F. (26.7° C. to 37. 8° C.) for one hour.

[0158] While stirring the above precursor solution, 850 lbs (386 kg) of600° C. Crosfield dehydrated silica carrier is added slowly to theprecursor solution and the mixture agitated for 30 min. at 80° F. to100° F. (26.7 to 37.8° C.). At the end of the 30 min. agitation of themixture, 240 lbs (109kg) of a 10 weight percent toluene solution ofAS-990 (N,N-bis(2-hydroxylethyl) octadecylamine ((Cl₈H₃₇N(CH₂CH₂OH)₂)available as Kemamine AS-990 from Witco Corporation, Memphis, Tenn., isadded together with an additional 110 lbs (50 kg) of a toluene rinse andthe reactor contents then is mixed for 30 min. while heating to 175° F.(79° C.). After 30 min. vacuum is applied and the polymerizationcatalyst mixture dried at 175° F. (79° C.) for about 15 hours to a freeflowing powder. The final polymerization catalyst weight was 1200 lbs(544 kg) and had a Zr wt % of 0.35 and an Al wt % of 12.0.

[0159] Process

[0160] A one liter 316 SS reactor with air-operated helical stirrer andan outer steam-heated shell and a inner acetone heat-transfer shell wasdried by heating to 115° C. while purging with 500 sccm of nitrogen for30 minutes. After cooling to 90° C., it was charged with 100 g ofpolyethylene (granular Union Carbide grade DSX4810 (available from UnionCarbide Corporation, Danbury, Conn.), Cr-based, 0.948 density, I₁₀=10,unstabilized) under inert conditions and pressure/vented four times with100 psi (690 kPa) nitrogen. A solution of 100 micromoles oftri-isobutylaluminum (TIBA) was then added and the reactor sealed andpressure/vented three times with 100 psi (690 kPa) ethylene beforebringing the reactor to reactor conditions, 80° C. and 107 psi (738kPa).

[0161] A catalyst charging vessel comprising a 1/4 inch (2 cm) SS tubeisolated between two valves and attached to a reservoir of nitrogen wascharged with 60.7 mg supported polymerization catalyst as describedabove in a nitrogen-filled glove box and attached to the reactor againsta nitrogen purge. The reactor was then pressurized and vented threetimes with ethylene. The reactor was then brought to 80° C., 107 psi(738 kPa) and the catalyst injected. After 38 minutes the temperaturewas ramped to 100° C. during 5 minutes and held for 40 minutes. Theideal acid compound for purposes of these experiments below will have noeffect on the catalyst activity at 80° C. but will substantially reducecatalyst activity at 100° C.

[0162] Table 1 represents the control experiments, where no acidcompound was used with the polymerization catalyst. Controls: Theseillustrate that without the acid, catalyst activity is substantial atthe higher temperature range, 100° C. in these examples. TABLE 1 Uptake% rate Activ- Rubble Uptake Uptake 100° C./ redn @ Ex. Acid ity¹ (%) 80°C. 100° C. 80° C. 20 min 1 none 11847  8% 14.9 31.3 2.1 −11%  2 none10595  6% 15.1 26.4 1.8 1% 3 none 13120  9% 17.9 30.3 1.7 −6%  4 none12401 28% 17.9 32.3 1.8 0% 5 none 12461 26% 16.2 31.5 1.9 −18%  6 none12461 18% 18.7 30.9 1.7 −6%  7 none 14219 15% 16.5 36.4 2.2 4% Average12443 16% 16.7 31.3 1.9 −5%  Standard  1110  9% 1.5 3.0 0.2 8% Deviation

Examples 8,9 and 10

[0163] 45 mg of L-malic acid was charged to the catalyst charging vesseland injected with nitrogen pressure at 20 minutes during the 80° C.segment of the run.

[0164] Table 2 illustrates the acid effect at the higher temperatures.Rubble is also reduced, indicating improved continuity. TABLE 2 Rub-Uptake % rate Activ- ble Uptake Uptake 100° C./ redn @ Ex. Acid ity¹ (%)80° C. 100° C. 80° C. 20 min 8 L-malic 7213 5% 13.40 15.52 1.16 −5% 9L-malic 8287 1% 12.96 22.25 1.72  0% 10  L-malic 13629  1% 13.88 30.822.22 −8%

[0165] For the following examples 11 to 20 also referto Table 3.

Examples 11 to 12

[0166] As in Example 8 except that the L-malic acid is mixed with thepolymerization catalyst. This illustrates a different mode of adding theacid is also effective.

Examples 13 to 15

[0167] As in Example 8 except that glutaric acid was used in place ofL-malic acid. This illustrates that a different acid is effective inreducing the polymerization rate at 100° C.

Example 16

[0168] As in Example 13 except only 23 mg of acid is used. Thisillustrates that t of inactivation is controlled by the amount of acidused.

Example 17

[0169] As in Example 13 except that the glutaric acid is mixed with thepolymerization catalyst. This illustrates another way of adding theacid.

Example 18

[0170] As in Example 16 except that the glutaric acid is mixed with thepolymerization catalyst. Again, this shows a different way to add theacid.

Example 19

[0171] As in Example 8 except that glutaric acid was used in place ofL-malic acid. This example illustrates the use of a different acid thateffectively reduces the polymerization rate at 100° C.

Example 20

[0172] As in Example 8 except that glutaric acid was used in place ofL-malic acid, lustrates using a different acid to effectively reduce thepolymerization rate at 100° C. TABLE 3 Rub- Uptake % rate Activ- bleUptake Uptake 100° C./ redn @ Ex. Acid ity¹ (%) 80° C. 100° C. 80° C. 20min  8 L-malic 7213 5% 13.40 15.52 1.16 7%  9 L-malic 8287 1% 12.9622.25 1.72 −5%  10 L-malic 13629  1% 13.88 30.82 2.22 0% 11 L-malic 55422% 11.27 12.27 1.09 — 12 L-malic 9300 2% 14.01 19.77 1.41 — 13 glutaric6026 5% 13.52 10.17 0.75 5% 14 glutaric 6781 5% 14.26 11.83 0.83 12%  15glutaric 8650 3% 13.65 18.44 1.35 10%  16 glutaric 10053  2% 15.84 20.921.32 8% 17 glutaric 7827 2% 12.82 13.62 1.06 — 18 glutaric 8979 2% 15.1216.90 1.12 −6%  19 3methyl 6555 9% 14.62 9.88 0.68 2% adipic 20 4-octyl-8445 5% 15.68 19.94 1.27 −10%  oxy- benzoic

[0173] While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that adifferent combination of acids may be used during the polymerizationprocess depending on the product being produced. Also, two or morepolymerization reactors, in series or parallel, slurry and/or gas phasemay be used in which different combinations of acid compounds may beused. Furthermore, the solid acid may be utilized downstream of thereactor to deactivate polymer withdrawn from a polymerization reactor.Also, two or more polymerization catalysts may be used with the acidcompound of the invention. For this reason, then, reference should bemade solely to the appended claims for purposes of determining the truescope of the present invention.

We claim:
 1. A catalyst composition comprising a polymerization catalystand a solid compound wherein the solid compound changes phase to asubstantially liquid state at a temperature above an operating reactiontemperature and wherein the compound in the liquid state reduces theeffectiveness of the polymerization catalyst to polymerize olefin(s). 2.The catalyst composition of claim 1 wherein the polymerization catalystis supported.
 3. The catalyst composition of claim 1 wherein the solidcompound has a weight loss of less than 20 weight percent measured usingthennogravimetric analysis at 80° C. for 20 minutes.
 4. The catalystcomposition of claim 1 wherein the solid compound has a dielectricconstant greater than
 2. 5. The catalyst composition of claim 1 whereinthe solid compound is an acid compound.
 6. The catalyst composition ofclaim 5 wherein the acid compound has at least one —OH functionality. 7.The catalyst composition of claim 5 wherein the acid compound is L-malicacid.
 8. The catalyst composition of claim 5 wherein the acid compoundis a Bronsted acid.
 9. A catalyst composition comprising a bulky ligandmetallocene catalyst compound, an activator, a support, and a solid acidcompound.
 10. The catalyst composition of claim 9 wherein the acidcompound is a Bronsted acid.
 11. The catalyst composition of claim 9wherein the catalyst composition is heated to greater than 65° C., thesolid acid compound forms a liquid.
 12. The catalyst composition ofclaim 9 wherein the catalyst composition is heated by heat generated bya polymerization process which is in excess of an operating reactiontemperature
 13. A method for preparing a catalyst composition comprisingthe steps of: a) combining a polymerization catalyst and an activator;and b) adding a solid polar compound to a) wherein the solid polarcompound is unreactive during the preparation.
 14. The method of claim13 wherein the solid polar compound is an acid compound.
 15. The methodof claim 13 further comprising adding a support.
 16. The method of claim15 wherein the support is added after step (a).
 17. The method of claim13 wherein the solid polar compound is unreactive above a polymerizationtemperature.
 18. The method of claim 13 wherein the polymerizationcatalyst is a bulky ligand metallocene catalyst compound.